CN102268154A - Thermally-reversible crosslinking of polymers - Google Patents
Thermally-reversible crosslinking of polymers Download PDFInfo
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- CN102268154A CN102268154A CN2011101150074A CN201110115007A CN102268154A CN 102268154 A CN102268154 A CN 102268154A CN 2011101150074 A CN2011101150074 A CN 2011101150074A CN 201110115007 A CN201110115007 A CN 201110115007A CN 102268154 A CN102268154 A CN 102268154A
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- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
Abstract
The invention relates to thermally-reversible crosslinking of polymers, concretely to a polymeric composition consisting essentially of (a) a free-radical degradable polymer selected from a degradable polymer and a free-radical crosslinked polymer, (b) a a free-radical inducing species; and (c) a free radical trapping species having at least a trapping site and a thermally-reversible bond connection site and including a hindered amine derivative stable organic free radical; and (d) a complementary thermally-reversible bond doner, including at least a functional group linked with the functional group of a second compound by a covalent bond, such that the covalent bond is a connection position point of the thermally-reversible and any one carbon bond; wherein the free radical trapping species suppresses degradation of the polymer in the presence of free-radical inducing species and is graftable onto the polymer at a trapping site after the polymer forms a free radical.
Description
The application is that international filing date is on December 24th, 2004, and international application no is PCT/US2004/043342, and name is called the dividing an application of Chinese patent application No.200480038888.2 of " Thermoinversion crosslink of polymkeric substance ".
Technical field
The present invention relates to carry out the polymeric system of free radical reaction, need to introduce the Thermoinversion crosslink that unique free radical causes therein.
Background technology
Many polymkeric substance can carry out free radical reaction.In these reactions some are deleterious, for example degraded or carbon-carbon crosslink.Make adverse reaction influence minimum in, need to promote the crosslinking reaction that linked reaction (rheology modified reaction) that (1) is favourable or (2) favourable free radical cause, wherein composition keeps melt processability.
Polyolefine often is subjected to non-selective free-radical chemistry effect.For example, the free-radical chemistry effect meeting under elevated temperature reduces molecular weight, is especially containing the polymkeric substance of tertiary hydrogen, for example in polypropylene and the polystyrene.In addition, free-radical chemistry effect meeting promotes carbon-carbon crosslink, causes unacceptable gel content of polyethylene and limited melt processability.
For polypropylene, the free radical cracking of polymkeric substance can be described as chain scission, and it reduces the molecular weight of polymkeric substance and improves its melt flow rate (MFR).Because chain rupture is inhomogeneous, along with forming the polymer chain that is known as the lower molecular weight of " end of the chain (tails) " in this area, molecular weight distribution improves.
For polyethylene, coupling of free radical carbon-to-carbon or cross-link bond have produced the polymkeric substance with limited melt processability.It is desirable to prepare and have the cross-linked polymer that improves melt processability.
Do not having chain rupture or making under the situation of polymkeric substance carbon-carbon crosslink, needing (1) to make various crosslinked polymers to keep melt processability by introducing crosslinked that unique free radical causes by making the polymkeric substance coupling improve the melt viscosity of various polymkeric substance and melt strength or (2).If polymkeric substance is halogenated, also need under the situation that does not make the polymkeric substance dehydrohalogenation, make polymkeric substance realize required coupling or crosslinking reaction.The key that unique free radical causes need be (thermally-reversible) of hot inversion.
Also need carry out the molecular structure of required when reaction controlling polymers at polymkeric substance.
Summary of the invention
The present invention be a kind of can be rheology modified polymeric composition or the polymeric composition of free-radical crosslinkable, rheology modified key that is wherein produced or cross-link bond are a kind of hot inversion keys.Resulting polymers by at least a when forming free radical the polymkeric substance of preferential degraded or carbon-carbon crosslink make.The present invention can make polymkeric substance by the coupling of hot inversion key or crosslinked in suppress preferential reaction.Suppress the reaction of unacceptable degraded or carbon-carbon crosslink and carry out required reaction, this produces rheology modification of polymers or free radical Thermoinversion crosslink polymkeric substance.
The present invention can be used for electric wire, footwear, film (greenhouse for example, shrink and Elastic Film), the engineering thermoplasties, high weighting material, fire retardant, reactive chemical combination, thermoplastic and high-elastic, Thermoplastic Vulcanizate, automobile, the vulcanized rubber substitute, buildings, automobile, furniture, foam materials, moistening, tackiness agent, paintable base material, polyolefine can dye, moisture curing, nano composite material, increase-volume, wax, calendered sheet, medical science, dispersion, coextrusion, cement/plastics reinforcement, food product pack, non-woven fabrics, the paper modification, laminated vessel, sports goods, oriented structure and surface-treatment applications.
Description of drawings
Fig. 1 has shown the temperature dependent form dynamic modulus of composition of the present invention and Comparative Examples.
Fig. 2 has shown the melt viscosity modulus of composition of the present invention and Comparative Examples.
Fig. 3 has shown the specific inductivity figure in the temperature range of composition of the present invention and Comparative Examples.
Fig. 4 has shown the dissipation factor figure in the temperature range of composition of the present invention and Comparative Examples.
Fig. 5 has shown the melt viscosity modulus of two kinds of compositions of the present invention and Comparative Examples.
Embodiment
" the hot inversion of FRTS--functional group's key " of Shi Yonging herein is meant the covalent linkage that forms between scavenger of free radicals (trapping species) and hot inversion functional group's donor (contributor).Before forming the hot inversion of FRTS--functional group's key, scavenger of free radicals contains at least one capture site and is connected (contribution) site with a hot inversion key.Capturing the site, scavenger of free radicals can be grafted on the polymer molecule.Connect (contribution) site at hot inversion key, scavenger of free radicals and hot inversion key donor covalency keyed jointing are to form hot inversion key.
" the hot inversion of FRTS--functional group's key " can be the part of the following keys: the hot inversion functional linkage of (1) carbon-FRTS-donor-carbon bond and the hot inversion-functional group of (2) carbon-FRTS--FRTS-carbon bond.Other example of key is conspicuous for those skilled in the art.Significantly, the hot inversion functional group more than can be arranged in the chain, and a plurality of hot inversion functional group can have different chemical structure (just, group can be dissimilar).
" limiting the catalytic polymkeric substance of catalyzer (constrained geometry catalyst) of geometrical shape ", " the catalytic polymkeric substance of CGC-" or the similar terms used are meant any polymkeric substance of making herein under the situation of the catalyzer that has the restriction geometrical shape.Used herein " catalyzer of restriction geometrical shape " or " CGC " have and U.S. Patent No. 5,272, in 236 and 5,278,272 to the definition of this term with identical implication is described.
For for example ethylene/alpha-olefin copolymer, " long chain branching (LCB) " of Shi Yonging is meant the short chain branch head's who produces than incorporating polymer backbone into by alpha-olefin chain length herein.Each long chain branches has identical comonomer distribution with polymer backbone, and can be the same with connected polymer backbone long.
" melt can be processed " of Shi Yonging is although be meant that polymkeric substance is crosslinked when solid-state herein, but in molten state, still keep the thermoplastic behavior---it is characterized in that polymkeric substance can flow in the viscosity mode, so polymkeric substance can for example be processed at traditional processing units in forcing machine and the shaping die.
Use herein " melt strength " is meant the maximum tension when fracture or draw resonance begin.Use adds available from the melt strength tester of Gottfert Inc. available from the capillary rheometer of Instron Corporation measures melt strength.Use capillary rheometer to make polymer melt pass through die head with constant through-rate.Use the melt strength tester to use nip rolls with 2.4 mm/second
2Acceleration uniaxial extension molten polymer silk.The required tension force that record and melt strength tester nip rolls derivation speed have functional relation.Capillary rheometer is furnished with 2.1 mm dias, 20: 1 die heads, and its inlet angle is about 45 °.Sample after 10 minutes, is being moved piston with the speed of 1 inch per minute clock 190 ℃ of balances.
" metallocenes " of Shi Yonging is meant metallic compound herein, and it contains at least one and is keyed to replacement or unsubstituted cyclopentadienyl on the metal." polymkeric substance of metallocene catalyst " or similar terms are meant and anyly have the polymkeric substance of making under the situation of metalloscene catalyst.
" polymolecularity " of Shi Yonging, " molecular weight distribution " and similar terms are meant weight-average molecular weight (M herein
w) and number-average molecular weight (M
n) ratio (M
w/ M
n).
" polymkeric substance " of Shi Yonging is meant the macromolecular cpd of making by the monomer polymerization of identical or different type herein." polymkeric substance " comprises homopolymer, multipolymer, terpolymer, interpretation (interpolymer), or the like.Term " interpretation " is meant the polymkeric substance of making by the polymerization of at least two kinds of monomers or comonomer.It comprises, but be not limited to, multipolymer (typically refers to the polymkeric substance of being made by two kinds of dissimilar monomers or comonomer, although it usually exchanges with " interpretation " and uses to censure by three kinds or the monomer of number of different types or the polymkeric substance that comonomer is made), terpolymer (it typically refers to the polymkeric substance of being made by three kinds of dissimilar monomers or comonomer), quaternary polymers (it typically refers to the polymkeric substance of being made by four kinds of dissimilar monomers or comonomer), and analogue.Term " monomer " or " comonomer " exchange and use, and they are meant in any adding reactor to make the compound that has polymerizable thing part of polymkeric substance.Be described as at polymkeric substance and comprise one or more monomers, for example comprise under the situation of polymkeric substance of propylene and ethene, polymkeric substance comprises certainly from these monomeric unit, for example-and CH
2-CH
2-, but not monomer itself, for example CH
2=CH
2
" P/E* multipolymer " that herein uses and similar terms are meant to have the propylene/unsaturated comonomer multipolymer of at least a following performance as feature: (i) corresponding with regio-error with about 15.7ppm about 14.6
13C NMR peak, these peaks have approximately identical intensity and the T in (ii) differential scanning calorimetric (DSC) curve
MeIdentical and the T of basic maintenance
PeakWith comonomer in the multipolymer, just from the unit of ethene and/or unsaturated comonomer, increase and reduce " T
Me" be meant the temperature when fusion finishes." T
Peak" be meant maximum melt temperature.Usually, the multipolymer in this embodiment is a feature to have these two performances simultaneously.U.S. Patent application series No.10/139 in that on May 5th, 2002 proposed describes these performances and their measuring methods separately in detail in 786 (WO2003040442) (it is incorporated herein by this reference).
These multipolymers can further have following characteristics---and have and be higher than approximately-1.20 index of skewness (skewness index), S
IxIndex of skewness is by getting available from the data computation of intensification elution fractionation (TREF).Data sheet is shown as the standard function figure of weight fraction and eluting temperature.The unitary molar content major decision of isotactic propylene eluting temperature.
The notable feature of curve shape is to compare curve shape hangover (tailing) under low eluting temperature with curve acutance or steepness under higher eluting temperature.The statistical value that reflects this asymmetry is a measure of skewness.Formula 1 mathematics has been represented the index of skewness as this asymmetry measurement standard, S
Ix
Value, T
Max, be meant in the TREF curve temperature in the maximum weight branch rate of 50 to 90 ℃ of wash-outs.T
iAnd w
iBe respectively i arbitrarily during TREF distributes
ThThe eluting temperature of fraction and weight fraction., make distribution stdn (w with respect to the total area at the curve of wash-out more than 30 ℃
iTotal amount equal 100%).Therefore, this index shape of reactive crystallization polymkeric substance only.From the calculating shown in the formula 1, ignore any not crystalline polymer (at 30 ℃ or be lower than 30 ℃ of polymkeric substance that still are in dissolved state).
The unsaturated comonomer of P/E* multipolymer comprises C
4-20Alpha-olefin, especially C
4-12Alpha-olefin, for example 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecylene etc.; C
4-20Diolefine, preferred 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB) and Dicyclopentadiene (DCPD); C
8-40Vinyl aromatic compounds, comprise vinylbenzene, neighbour, and p-methylstyrene, Vinylstyrene, vinyl biphenyl, vinyl naphthalene; C with the halogen replacement
8-40Vinyl aromatic compounds, for example chloro-styrene and fluorobenzene ethene.Ethene and C
4-12Alpha-olefin is preferred comonomer, and ethene is particularly preferred comonomer.
The P/E* multipolymer is unique subclass of P/E multipolymer.The P/E multipolymer comprises all multipolymers of propylene and unsaturated comonomer, and is not only the P/E* multipolymer.P/E multipolymer beyond the P/E* multipolymer comprises the multipolymer and the catalytic multipolymer of Z-N-of catalyst of multipolymer, the finite geometry shape of metallocene catalyst.For the present invention, the P/E multipolymer contains 50 weight % or more propylene, and EP (ethylene-propylene) multipolymer contains 51 weight % or more ethene." the containing ... propylene " of Shi Yonging, " containing ... ethene " and similar terms are meant that polymkeric substance contains the unit from propylene, ethene or analogue herein, but not compound itself.
The polymkeric substance that " alfon " and similar terms only are meant or almost all are made of the unit from propylene." polypropylene copolymer " and similar terms are meant and comprise from the unit of propylene and ethene and/or the polymkeric substance of one or more unsaturated comonomers.
" rheology modified " of Shi Yonging is meant the change of the polymer malt viscosity of measuring by dynamic mechanical spectroscopy (DMS) herein.For the low-shear viscosity that under shear viscosity that records under the shearing of 100 rad/seconds (rad/sec) and shearing, records at 0.1rad/sec, the change of evaluation and test melt viscosity.
According to the desirably polymer-modified rheology of the present invention, thereby under the situation of the approximately identical shear viscosity of maintenance, improve melt strength.That is to say, compare that rheology modified polymkeric substance shows higher stretch-resistance under low shearing condition in the process that molten polymer extends, but do not sacrifice the work output under the shear conditions with stock polymer.In the present invention, it is desirable to, the viscosity under low shearing condition is compared raising about at least 5% with stock polymer.When in polymkeric substance, adding long chain branches or similar structures, observe the raising of melt strength usually.
Perhaps, can the rheology according to the polymkeric substance of modification of the present invention be described with the ratio (" low/shear viscosity ratio ") of low-shear viscosity and shear viscosity.Especially, rheology modified polymkeric substance of the present invention can have following characteristics---and low/shear viscosity is than the low/shear viscosity ratio that is higher than its stock polymer.Preferably, low/shear viscosity more preferably improves at least 10% than improving at least 5%, preferred again raising at least 20%.In addition, preferably, when keeping or reducing shear viscosity, improve low/shear viscosity ratio.More preferably, in the higher relatively shear viscosity of maintenance, improve low/shear viscosity ratio.When in polymkeric substance, adding long chain branches or similar structures, observe the raising of low/shear viscosity ratio usually.
Perhaps and preferably, no matter rheology modified polymkeric substance whether with its melt strength or its low/the shear viscosity ratio is a feature, the gained rheology modification of polymers has and is lower than about 10 weight %, more preferably less than the gel content that hexanaphthene extraction (ASTM 2765) records that passes through of about 5 weight %.Equally preferably, the gel content of rheology modification of polymers is compared with the gel content of stock polymer (unmodified polymer), and the absolute value that exceeds is less than 5 weight %.
Cross-linked polymer has 10 weight % or higher, preferred 30 weight % or higher, and more preferably do 50 weight % or the higher hexanaphthene that passes through extract the gel content (ASTM that records?).
" hot inversion key " or " hot inversion functional group " is meant that the chemistry between two functional groups that produced by temperature dependent balanced class chemical reaction connects as used herein, wherein chemistry connects formation at low temperatures, but breaks along with temperature raises reversibly to produce.The example of hot inversion functional group comprises urethanum, urea, azlactone, maleimide-furans Diels-Alder adduct and other Diels-Alder adduct.
" hot inversion key donor " is meant following compound as used herein, it contains the functional group of functional group's covalency keyed jointing of (a) at least one and second compound, making the gained covalent linkage is hot inversion key (" hot inversion key connect (contribution) site ") and (b) randomly, a carbon bond connects the site.For example, 4-hydroxyl TEMPO and diphenylmethanediisocyanate (methylene diphenyl diisocyanate) are that the hot inversion key donor that replenishes is to form hot inversion urethane bonds.4-hydroxyl TEMPO produces hydroxyl, and diphenylmethanediisocyanate produces isocyanate groups.Significantly, 4-hydroxyl TEMPO contains at least one to capture site (just carbon bond connects the site) and contain the example that hot inversion key connects the scavenger of free radicals in (contribution) site.Diphenylmethanediisocyanate has two and can be used as the functional group that hot inversion key connects (contribution) site.Connect the quantity in (contribution) site according to its hot inversion key, hot inversion key donor can with other donor keyed jointing to form extra hot inversion key.
" Z-N-catalytic polymkeric substance ", " the catalytic polymkeric substance of Z-N-" or similar terms are meant and anyly have the polymkeric substance of making under the situation of Ziegler-Natta catalyst.
In an embodiment, the present invention be can be rheology modified polymeric composition or the polymeric composition of free-radical crosslinkable, they comprise free radical reaction polymkeric substance, free radical evocating substance, contain at least one capture site is connected (contribution) site with a hot inversion key scavenger of free radicals and additional hot inversion key donor.Polymkeric substance can form free radical when being caused by the free radical evocating substance.
The free radical reaction polymkeric substance comprises free radical degradable polymer and free-radical crosslinkable polymers.When the free radical reaction polymkeric substance was the free radical degradable polymer, polymkeric substance carried out DeR when not having scavenger of free radicals and being caused by the free radical evocating substance.DeR can be chain rupture or dehydrohalogenation.Scavenger of free radicals fully suppresses DeR and can be grafted on the polymkeric substance behind the polymer formation free radical.When having hot inversion key connection (contribution) site, scavenger of free radicals can react to form hot inversion key with the hot inversion key donor that replenishes.
When the free radical reaction polymkeric substance was free-radical crosslinkable polymers, polymkeric substance carried out the carbon-carbon crosslink reaction when not having scavenger of free radicals and being caused by the free radical evocating substance.Scavenger of free radicals fully suppresses the carbon-carbon crosslink reaction and can be grafted on the polymkeric substance behind the polymer formation free radical.
Can use multiple free radical degradable polymer as polymkeric substance in the present invention.The free radical degradable polymer can be alkyl (hydrocarbon-based).Suitable free radical degradable hydrocarbyl polymers comprises polymkeric substance, vinyl chloride-base polymer and their blend of isoprene-isobutylene rubber, polyacrylic rubber, polyisobutene, alfon, propylene copolymer, styrene/butadiene/styrene block copolymers, styrene/ethylene/butadiene/styrene copolymers, vi-ny l aromatic monomers.
Preferably, free radical degradable hydrocarbyl polymers is selected from iso-butylene, propylene and styrene polymer.
Preferably, isoprene-isobutylene rubber of the present invention is the multipolymer of iso-butylene and isoprene.Isoprene is usually with the amount use of about 1.0 weight % to about 3.0 weight %.
The example of available propene polymer comprises alfon and P/E multipolymer in the present invention.Especially, these propene polymers comprise polypropylene elastomers.Propene polymer can be made by any method and can pass through Z-N, CGC, metallocenes and non-metallocene, the manufacturing of metal middle (metal-centered) heteroaryl ligands catalysis method.
That the available propylene copolymer comprises is random, block and graft copolymer.Exemplary propylene copolymers comprises Exxon-Mobil VISTAMAX, Mitsui TAFMER and the VERSIFY of The Dow Chemical Company
TMIt is about at least 0.850 that the density of these multipolymers is generally, preferably about at least 0.860, more preferably about at least 0.865 gram/cubic centimetre (g/cm
3).
Usually, the maximum density of these propylene copolymers is about 0.915, and is preferred maximum about 0.900, more preferably maximum about 0.890 gram/cubic centimetre.The weight-average molecular weight of these propylene copolymers (Mw) can in very large range change, but usually about 10,000 to 1,000, between 000.The polymolecularity of these multipolymers is usually between about 2 to about 4.
It is about at least 0.01 that these propylene copolymers have usually, preferably about at least 0.05, more preferably about at least 0.1 melt flow rate (MFR) (MFR).It is about 2000 that maximum MFR is no more than usually, and preferably it is no more than approximately 1000, more preferably no more than about 500, further preferably is no more than approximately 80, is most preferably not exceeding about 50.According to ASTM D-1238, condition L (2.16 kilograms, 230 ℃) measures propylene and ethene and/or one or more C
4-C
20The MFR of the multipolymer of alpha-olefin.
The available styrene/butadiene/styrene block copolymers is a phase-separated system among the present invention.Styrene/ethylene/butadiene/styrene copolymers also can be used for the present invention.
The polymkeric substance of vi-ny l aromatic monomers can be used for the present invention.Suitable vi-ny l aromatic monomers includes, but not limited to become known for those vi-ny l aromatic monomers of polymerization process, and for example U.S. Patent No. 4,666, those that describe in 987,4,572,819 and 4,585,825.
Preferably, monomer has following formula:
Wherein R ' is hydrogen or contains three or the alkyl of carbon still less, Ar is the aromatic ring structure that contains 1 to 3 aromatic ring, have or do not have alkyl, halogen or alkylhalide group substituting group, wherein any alkyl contains 1 to 6 carbon atom and alkylhalide group is meant the alkyl that halogen replaces.Preferably, Ar is phenyl or alkyl phenyl, and wherein alkyl phenyl is meant the phenyl that alkyl replaces, and wherein phenyl most preferably.Operable typical vinyl aromatic monomers comprises: all isomer of vinylbenzene, alpha-methyl styrene, Vinyl toluene, and particularly to all isomer, propylstyrene, vinyl biphenyl, vinyl naphthalene, vinyl anthracene and analogue and their mixture of Vinyl toluene, ethyl styrene.
Vi-ny l aromatic monomers can also combine with other copolymerisable monomer.These monomeric examples include, but are not limited to Acrylic Acid Monomer, for example vinyl cyanide, methacrylonitrile, methacrylic acid, methyl methacrylate, vinylformic acid and methyl acrylate; Maleimide, phenyl maleimide and maleic anhydride.In addition, can to carry out polymerization under the pre-molten elastomeric situation impact modified to prepare existing, or contain the product of graft rubber, at United States Patent(USP) Nos. 3,123, these examples have been described in 655,3,346,520,3,639,522 and 4,409,369.
The present invention also is applicable to rigidity, matrix (matrix) or the continuous phase polymer of rubber modified monovinylidene aromatic polymers composition.
Can use multiple free radical carbon-to-carbon crosslinkable polymer as polymkeric substance in the present invention.Polymkeric substance can be an alkyl.Suitable free radical carbon-to-carbon crosslinkable hydrocarbyl polymers comprises acronitrile-butadiene-styrene rubber, neoprene, chlorosulfonated polyethylene rubber, ethylene/alpha-olefin copolymer, ethene/diene copolymers, Alathon, ethylene/propylene/diene monomer, ethylene/propylene rubber, the ethylene/styrene interpolymers polymers, ethene/unsaturated ester multipolymer, fluoropolymer, halogenated polyethylene, hydrogenated nitrile-butadiene rubber, natural rubber, paracril, polybutadiene rubber, silicon rubber, styrene/butadiene rubbers, styrene/butadiene/styrene block copolymers, styrene/ethylene/butadiene/styrene copolymers and their blend.
For the present invention, neoprene is the polymkeric substance of chlorbutadiene normally.Preferably, make rubber by letex polymerization.In addition, can carry out polymerization under the situation of sulphur so that in polymkeric substance, introduce crosslinked existing.
Preferably, free radical carbon-to-carbon crosslinkable hydrocarbyl polymers is an ethene polymers.
For suitable ethene polymers, polymkeric substance belongs to four kinds of main types usually: (1) is highly branched; (2) heterogeneous line style; (3) homogeneously branched line style; (4) homogeneously branched substantial linear.These polymkeric substance can be used Ziegler-Natta catalyst, metallocenes or vanadium base single-point catalyst or limit the single-point catalyst preparation of geometrical shape.
Highly branched ethene polymers comprises new LDPE (film grade) (LDPE).These polymkeric substance can prepare under high temperature and high pressure with radical initiator.Perhaps, they can prepare under high temperature and relatively low pressure with coordination catalyst.These polymkeric substance have about 0.910 gram/cubic centimetre of recording by ASTM D-792 density to about 0.940 gram/cubic centimetre.
Heterogeneous linear ethylene polymkeric substance comprises LLDPE (LLDPE), ultra-low density polyethylene (ULDPE), very low density polyethylene (VLDPE) and high density polyethylene(HDPE) (HDPE).The linear, low density ethene polymers has about 0.850 gram/cubic centimetre to the density of about 0.940 gram/cubic centimetre with pass through ASTM 1238, and condition I records about 0.01 to about 100 restrains/10 minutes melt index.Preferably, melt index be about 0.1 to about 50 the gram/10 minutes.In addition, preferably, LLDPE is that ethene and one or more contain 3 to 18 carbon atoms, the more preferably interpretation of other alpha-olefin of 3 to 8 carbon atoms.Preferred comonomer comprises 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene.
Ultra-low density polyethylene and very low density polyethylene are known interchangeable.These polymkeric substance have the density of about 0.870 gram/cubic centimetre to about 0.910 gram/cubic centimetre.High density ethylene polymer normally density is the homopolymer of about 0.941 gram/cubic centimetre to about 0.965 gram/cubic centimetre.
Homogeneously branched linear ethylene polymkeric substance comprises homogeneous phase LLDPE.Evenly branching/homogeneous polymer is following compound---comonomer random distribution in given interpretation molecule wherein, and wherein the interpretation molecule has similar ethene/comonomer ratio in this interpretation.
Homogeneously branched substantially linear ethylene polymers comprises (a) C
2-C
20Alkene, for example homopolymer of ethene, propylene and 4-methyl-1-pentene, (b) ethene and at least a C
3-C
20Alpha-olefin, C
2-C
20Acetylene series unsaturated monomer, C
4-C
18The interpretation of diolefine or these monomeric binding substancess and (c) ethene and at least a C
3-C
20Alpha-olefin, diolefine or with the interpretation of other unsaturated monomer bonded acetylene series unsaturated monomer.These polymkeric substance have the density of about 0.850 gram/cubic centimetre to about 0.970 gram/cubic centimetre usually.Preferably, density is extremely about 0.955 gram/cubic centimetre of about 0.85 gram/cubic centimetre, and more preferably about 0.850 gram/cubic centimetre is to 0.920 gram/cubic centimetre.
Available ethylene/styrene interpolymers polymers comprises the random substantially interpretation by olefinic monomer (just ethene, propylene or 'alpha '-olefin monomers) and vinylidene aromatic monomer, hindered aliphatic vinylidene monomer or alicyclic vinylidene monomer polymerization are made among the present invention.Suitable olefinic monomer contains 2 to 20, and is preferred 2 to 12, more preferably 2 to 8 carbon atoms.Preferred this monomer comprises ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene.Most preferably ethene and ethene and propylene or C
4-8The combination of alpha-olefin.Randomly, ethylene/styrene interpolymers polymers polymeric component can also comprise ethylenically unsaturated monomers, for example strain (strained) cyclic olefin.The example of strain cyclic olefin comprises norbornylene and C
1-10Alkyl or C
6-10The norbornylene that aryl replaces.
Available ethene/unsaturated ester multipolymer can be by conventional pressure technique preparation among the present invention.Unsaturated ester can be alkyl acrylate, alkyl methacrylate or vinyl carboxylates.Alkyl can contain 1 to 8 carbon atom, and preferably contains 1 to 4 carbon atom.The carboxylate group can be contained 2 to 8 carbon atoms, and preferably contains 2 to 5 carbon atoms.The multipolymer part that produces by the ester comonomer can account for multipolymer weight about 5 to about 50 weight %, and preferably approximately 15 is to about 40 weight %.The example of acrylate and methacrylic ester is ethyl propenoate, methyl acrylate, methyl methacrylate, tert-butyl acrylate, n-butyl acrylate, n-BMA and 2-EHA.The example of vinyl carboxylates is vinyl-acetic ester, propionate and vinyl butyrate.The melt index of ethene/unsaturated ester polymkeric substance can for about 0.5 to about 50 the gram/10 minutes.
Among the present invention the available halogenated vinyl polymer comprise fluoridize, chlorination and brominated olefin polymers.The raw material olefin polymkeric substance can be homopolymer or the interpretation that contains the alkene of 2 to 18 carbon atoms.Preferably, olefin polymer be ethene and propylene or with the interpretation of the alpha-olefin that contains 4 to 8 carbon atoms.Preferred alpha-olefin comonomer comprises 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene.Preferably, halogenated olefin polymer is a chlorinatedpolyethylene.
Suitable natural rubber comprises the high-molecular weight polymer of isoprene among the present invention.Preferably, natural rubber has about 5000 number-average degree of polymerization and wide molecular weight distribution.
Preferably, paracril of the present invention is the random copolymers of divinyl and vinyl cyanide.
The available polybutadiene rubber is preferably 1 among the present invention, the homopolymer of 4-divinyl.
The available styrene/butadiene rubbers comprises the random copolymers of vinylbenzene and divinyl.Usually, make these rubber by radical polymerization.Styrene/butadiene/styrene block copolymers of the present invention is a phase-separated system.Styrene/ethylene/butadiene/styrene copolymers also can be used for the present invention.
Available free radical evocating substance comprises organo-peroxide, azo free radical evocating substance and two cumenes.Preferably, the free radical evocating substance is an organo-peroxide.In addition, oxygen-enriched environment is preferred for causing useful free radical.Preferred organo-peroxide comprises dicumyl peroxide, Vulcup R and dialkyl peroxide.More preferably, organo-peroxide is to be selected from 2,5-two (t-butylperoxy)-2,5-dimethylhexane and 2,5-two (t-butylperoxy)-2, the dialkyl peroxide of 5-dimethyl-3-hexin.Most preferably, organo-peroxide is 2,5-two (t-butylperoxy)-2,5-dimethyl-3-hexin.
Organo-peroxide can add by direct injection.Preferably, the amount of free radical evocating substance is extremely about 20.0 weight % of about 0.005 weight %, and more preferably about 0.01 weight % is to about 10.0 weight %, and most preferably about 0.03 weight % is to about 5.0 weight %.
Except that the free radical evocating substance or replace the free radical evocating substance, polymkeric substance can also can, form free radical when heat or radiation being subjected to shearing.Therefore, shear the effect that energy, heat or radiation can be played the free radical evocating substance.In addition, show under the situation that has the free radical that is generated by aforementioned free radical evocating substance as scavenger of free radicals, scavenger of free radicals can exist by shearing and can, play a role under the situation of the free radical of heat or radiation generation.
Think when producing free radical, need combining of scavenger of free radicals and radical source for the coupling of polymkeric substance by organo-peroxide, oxygen, air, shearing energy, heat or radiation.This bonded control has been determined the molecular configuration of coupling polymer (rheology modification of polymers just).The continuous interpolation of scavenger of free radicals causes free radical then gradually, thereby the unprecedented degree of control to molecular configuration is provided.
Also think and on polymkeric substance, also to use the scavenger of free radicals end-blocking to form the stable free radical in side (pendant) in the initiation grafting site.Subsequently, the stable free radical in side can react with the hot inversion key donor that replenishes, to produce required degree of uniformity.
The example of available scavenger of free radicals comprises that the hindered amine deutero-stablizes organic free radical among the present invention.Preferably, when scavenger of free radicals is a hindered amine deutero-when stablizing organic free radical, it is 2,2,6, the hydroxy derivatives of 6-tetramethyl-piperidyl oxygen (TEMPO).More preferably, scavenger of free radicals is 4-hydroxyl-TEMPO.
Preferably, the amount of scavenger of free radicals is extremely about 20.0 weight % of about 0.005 weight %, and more preferably about 0.01 weight % is to about 10.0 weight %, and most preferably about 0.03 weight % is to about 5.0 weight %.
Preferably, the concentration of the ratio of free radical evocating substance and scavenger of free radicals and scavenger of free radicals promotes the polymkeric substance coupling.More preferably, free radical evocating substance and scavenger of free radicals to exist ratio to be higher than about 1, more preferably about 20: 1 to about 1: 1.
Scavenger of free radicals and free radical evocating substance can combine with polymkeric substance in many ways, comprise direct chemical combination, direct impregnation and direct injection.
The hot inversion key donor that replenishes comprises the compound that contains the functional group that is fit to the hot inversion of preparation functional group, for example urethanum, urea, azlactone, maleimide-furans Diels-Alder adduct and other Diels-Alder adduct.For example, when scavenger of free radicals contained hydroxyl as its hot inversion key connection (contribution) site, additional hot inversion key donor can be an isocyanic ester.Useful especially isocyanic ester comprises vulcabond or polymerization vulcabond among the present invention.Preferably, vulcabond is selected from aliphatic series and aromatic diisocyanate.The aliphatic vulcabond that is fit to comprises hexamethylene diisocyanate.More preferably, vulcabond is the aromatic diisocyanate that is selected from diphenylmethanediisocyanate, polymerization diphenylmethane diisocyanate and tolylene diisocyanate.
In another embodiment, the present invention is a kind of method for preparing the free-radical crosslinkable polymeric composition.The first step of this method is to prepare the polymer-matrix mixture by mixing its component.Component comprises free radical reaction polymkeric substance, free radical evocating substance, contains at least one capture site is connected (contribution) site with a hot inversion key scavenger of free radicals and additional hot inversion key donor.Scavenger of free radicals fully suppresses unacceptable reaction.In second step, polymkeric substance is crosslinked by scavenger of free radicals.
In a preferred embodiment, the present invention is the goods of being made by the polymeric composition of polymeric composition that can be rheology modified or free-radical crosslinkable.Can make and prepare these goods in many ways.Especially the available method comprise injection forming, extrude, pressing mold, rotational molding, thermoforming, blowing, powder coated, Banbury (Banbury) intermittent type Banbury mixer, fiber sprinning and calendering.
Suitable goods comprise the wire cable insulating body, the electric wire semiconductor article, electric wire coating and big envelope, cable fitting, sole, polycomponent sole (polymkeric substance that comprises different densities and type), windproof waterproof cloth (weather stripping), packing ring, section bar, dutiable goods, rigidity super drawing band, run flat tire (run flat tire) inset, building panel (construction panels), matrix material (for example Wood composite material), tubing, foam, blown film and fiber (comprising adhesive fiber and spandex fiber).
Embodiment
Following non-limiting examples has been explained the present invention.
Comparative Examples 1-2 and embodiment 3
With melt index is 2.4 grams/10 minutes, I21/I2 is 52, density be 0.9200 gram/cubic centimetre, polymolecularity (Mw/Mn) be 3.54 and fusing point be that 110.2 ℃ new LDPE (film grade) prepares two Comparative Examples of the present invention and an embodiment.
Before mixing, with polyethylene vacuum-drying to remove any residue moisture.In the Brabender mixing tank the every kind formulation (do not comprise superoxide) of 125 ℃ of preparations shown in the Table I 3 minutes to make 40 gram samples.Add superoxide subsequently.With composition recombination 4 minutes.With the mixing tank nitrogen purging.
The DXM-446 new LDPE (film grade) is available from The Dow Chemical Company.Use synthetic MDI urethanum-TEMPO (MDI UBT) affixture of diphenylmethanediisocyanate and 4-hydroxyl TEMPO (can available from A.H.Marks).Luperox
TM1012,5-two (t-butylperoxy)-2,5-dimethylhexane organo-peroxide is available from Atofina.
Use dynamic mechanical spectra meter (DMS) research reaction kinetics.Carry out the DMS test on the controlled strain rheometer of the ARES that carries out twisting test (TA instruments) being furnished with two cantilever anchor clamps.
160 ℃ of pressing molds 2 hours to guarantee Luperox
TM101 organo-peroxides decompose fully, thus the preparation sample.Suppress 1.5 millimeters plates and be cut into the bar of 32 millimeters * 12 millimeters of sizes.
Then the sample two ends all are clipped between the anchor clamps of 10 millimeters at interval (clamping spacing (grip separation) Δ L), and carry out the heating step gradually of from 30 ℃ to 220 ℃ (2 ℃ of every steps).Under each temperature, measure torsion modulus G ' and G down with the angular frequencys of 10 rad/seconds (rad/s) ", between strain amplitude remains on 0.1% to 3% to guarantee that the enough and measuring result of torque keeps linear.The initial static(al)s (since stretch pattern) that keep 10 grams lax when preventing that sample from producing thermal expansion.Thus, clamp separation delta L and improve, particularly be higher than the temperature of fusing point or softening temperature with temperature.Stop test when reaching 65 millimeters in maximum temperature or the gap between anchor clamps.Fig. 1 has shown the temperature dependent form dynamic modulus of exemplary composition.
Measure gel content by the hexanaphthene extraction.With sample in moving die rheometer (MDR) with 160 ℃, the arc processing of the frequency of 100 cycles/minute and 0.5 degree 80 minutes, preparation is used for the sample of hexanaphthene extraction thus.About 5 grams of samples weighed also place Mylar
TMBetween the plate, place MDR then.The result is presented in the Table I.
Shear the shear-thinning behavior of evaluating and testing Comparative Examples 1 and embodiment 3 at 220 ℃ by dynamic oscillation.With sample in press with 160 ℃ of pressing molds 100 minutes.Do not evaluate and test Comparative Examples 2, because it is heat cured.Each frequency sweep finish about 15 minutes of cost (comprise initial be issued to equilibrated about 3 minutes) in test temperature.140 ℃, 180 ℃ and 220 ℃ of evaluation and test Comparative Examples 1.At 220 ℃ of evaluation and test embodiment 3.Fig. 2 has shown the melt viscosity of Comparative Examples 1 and embodiment 3.
Table I
4-hydroxyl-TEMPO grafting of LDPE
Use 4-hydroxyl TEMPO, DXM-446 new LDPE (film grade) and Luperox
TM130 2,5-two (t-butylperoxy)-2,5-dimethyl-3-hexin organo-peroxide prepares the 4-hydroxyl-TEMPO grafting of new LDPE (film grade).4-hydroxyl TEMPO is available from A.H.Marks.New LDPE (film grade) is available from The Dow Chemical Company.Luperox
TM130 2,5-two (t-butylperoxy)-2,5-dimethyl-3-hexin organo-peroxide is available from Atofina.
4-hydroxyl-the TEMPO of five (5) weight % and the new LDPE (film grade) of 92.5 weight % are restrained in the Bradender mixing tanks 125 ℃ of fusings (fluxed) 3 minutes 250.Next, add 2.5 weight % organo-peroxides.With composition recombination 4 minutes.Temperature is risen to 180 ℃ then.Mix again and continue 150 minutes.Use the nitrogen purging mixing tank continuously.
The LDPE of Thermoinversion crosslink
At first the 4-hydroxyl-TEMPO grafted new LDPE (film grade) that will as above make in 250 gram Brabender mixing tanks prepares the new LDPE (film grade) of Thermoinversion crosslink thus 125 ℃ of fusings 3 minutes.Next, add 4 weight % diphenylmethanediisocyanates, composition remix 4 minutes.Use the nitrogen purging mixing tank continuously.
With Thermoinversion crosslink LDPE 140 ℃ of pressing molds 180 minutes to make the plate of 50 mil thick.Thermoinversion crosslink LDPE contains 80% gel that records by hexanaphthene extraction.
As embodiment 6, Thermoinversion crosslink LDPE and Comparative Examples 4 and 5 are compared.The prescription of Comparative Examples is presented in the Table II.Physics evaluation and test (comprising aging result) is listed in the Table II.
For ageing research, Thermoinversion crosslink LDPE was at room temperature worn out for 7 weeks with the form of 115 mils (0.115 inch) slab.Then plate was solidified 2 hours with the arc of 140 ℃, the frequency of 100 cycles/minute and 0.5 degree in moving die rheometer.
For Comparative Examples 4 and 5 and embodiment 6, be presented in Fig. 3 and 4 in about 25 ℃ of specific inductivity and dissipation factors to about 90 ℃ temperature range.
Shear the shear-thinning behavior of evaluating and testing Comparative Examples 1, embodiment 3 and embodiment 6 at 220 ℃ by dynamic oscillation.With sample in press with 140 ℃ of pressing molds 180 minutes.Carry out frequency sweep twice.Each frequency sweep finish about 15 minutes of cost (comprise initial be issued to equilibrated about 3 minutes) in test temperature.At 220 ℃ of evaluation and test Comparative Examples 1, embodiment 3, embodiment 6 (passing through for the first time) and embodiment 6 (passing through for the second time).Fig. 5 has shown melt viscosity.
Table II
Claims (12)
1. polymeric composition, it comprises:
A) free radical reaction polymkeric substance, it is selected from free radical degradable polymer and free-radical crosslinkable polymers,
B) free radical evocating substance,
C) contain the scavenger of free radicals that at least one captures a site and a hot inversion key connection site, described scavenger of free radicals comprise the hindered amine deutero-stablize organic free radical and
D) the hot inversion key donor of Bu Chonging, the functional group that it contains functional group's covalency keyed jointing of at least one and second compound, make the gained covalent linkage be hot inversion key and randomly a carbon bond connect the site,
Wherein said scavenger of free radicals fully suppresses polymer degradation under the situation that has the free radical evocating substance, and behind the polymer formation free radical, capturing the site, can be grafted on the polymkeric substance.
2. polymeric composition according to claim 1, wherein said free radical degradable polymer carry out DeR when not having scavenger of free radicals and being caused by the free radical evocating substance.
3. polymeric composition according to claim 2, wherein said DeR are chain rupture or dehydrohalogenation DeR.
4. polymeric composition according to claim 2, wherein said free radical degradable polymer is the alkyl radical degradable polymer.
5. polymeric composition according to claim 4, wherein said free radical degradable polymer are selected from polymkeric substance, vinyl chloride-base polymer and their mixture of isoprene-isobutylene rubber, polyacrylic rubber, polyisobutene, alfon, propylene copolymer, styrene/butadiene/styrene block copolymers, styrene/ethylene/butadiene/styrene copolymers, vi-ny l aromatic monomers.
6. polymeric composition according to claim 1, wherein said free-radical crosslinkable polymers are free radical carbon-to-carbon crosslinkable polymer, and it carries out the carbon-carbon crosslink reaction when not having scavenger of free radicals and being caused by the free radical evocating substance.
7. polymeric composition according to claim 1, wherein said free-radical crosslinkable polymers are alkyl.
8. polymeric composition according to claim 6, wherein said free radical carbon-to-carbon crosslinkable polymer are alkyl.
9. polymeric composition according to claim 8, wherein free radical carbon-to-carbon crosslinkable hydrocarbyl polymers is selected from acronitrile-butadiene-styrene rubber, neoprene, chlorosulfonated polyethylene rubber, ethylene/alpha-olefin copolymer, ethene/diene copolymers, Alathon, ethylene/propylene/diene monomer, ethylene/propylene rubber, the ethylene/styrene interpolymers polymers, ethene/unsaturated ester multipolymer, fluoropolymer, halogenated polyethylene, hydrogenated nitrile-butadiene rubber, natural rubber, paracril, polybutadiene rubber, silicon rubber, styrene/butadiene rubbers, styrene/butadiene/styrene block copolymers, styrene/ethylene/butadiene/styrene copolymers, and composition thereof.
10. polymeric composition according to claim 1, wherein said free radical evocating substance are selected from organo-peroxide, azo free radical evocating substance, two cumenes and composition thereof.
11. polymeric composition according to claim 1, wherein said scavenger of free radicals is stablized organic free radical for the hindered amine deutero-.
12. polymeric composition according to claim 1, wherein said hot inversion key donor is selected from urethanum, urea, azlactone, maleimide-furans Diels-Alder adduct, other Diels-Alder adduct, and composition thereof.
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| CNA2004800388863A Pending CN1898336A (en) | 2003-12-24 | 2004-12-24 | Rheological improvement of polymer |
| CN2011101150074A Pending CN102268154A (en) | 2003-12-24 | 2004-12-24 | Thermally-reversible crosslinking of polymers |
| CNA2004800388882A Pending CN1898338A (en) | 2003-12-24 | 2004-12-24 | Thermoinversion crosslink of polymer |
| CNA2004800419698A Pending CN1918236A (en) | 2003-12-24 | 2004-12-24 | Free-radical crosslinkable polymers: improved process for crosslinking and compositions |
| CNA2004800389870A Pending CN1898339A (en) | 2003-12-24 | 2004-12-24 | Free radical initiated polymer crosslink |
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| CNA2004800389870A Pending CN1898339A (en) | 2003-12-24 | 2004-12-24 | Free radical initiated polymer crosslink |
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| KR20200100091A (en) | 2017-12-18 | 2020-08-25 | 보레알리스 아게 | Polyethylene with high vinyl content and beneficial rheological properties |
| CN111492444B (en) | 2017-12-18 | 2022-06-14 | 博里利斯股份公司 | Cable made of a crosslinkable composition free of antioxidants and having advantageous methane formation |
| WO2019121720A1 (en) | 2017-12-18 | 2019-06-27 | Borealis Ag | Cable made from crosslinkable composition without antioxidant and beneficial methane formation with reduced crosslinking |
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| CN114502602B (en) * | 2019-09-30 | 2024-02-06 | 埃克森美孚化学专利公司 | High pressure polyethylene tubular reactor process for improved wire coating products |
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| WO2024015604A1 (en) * | 2022-07-15 | 2024-01-18 | Dow Global Technologies Llc | Process for reversible crosslink composition |
| WO2024031619A1 (en) * | 2022-08-12 | 2024-02-15 | Dow Global Technologies Llc | Air curable ethylene/alpha-olefin interpolymer compositions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040059060A1 (en) * | 1999-09-16 | 2004-03-25 | Keisuke Chino | Thermo-reversible, crosslinkable elastomer and composition thereof |
| CN1527815A (en) * | 2001-05-17 | 2004-09-08 | ���з��ɹ�˾ | Organic peroxide heat stabliser |
Family Cites Families (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3123655A (en) | 1964-03-03 | Process for extruding high impact thermoplastic | ||
| US3346520A (en) | 1965-01-25 | 1967-10-10 | Dow Chemical Co | Process for making high impact styrene polymers in aqueous suspension |
| US3639522A (en) | 1969-06-04 | 1972-02-01 | Dow Chemical Co | Self-extinguishing high impact styrene polymers |
| JPS4838219B1 (en) * | 1970-12-30 | 1973-11-16 | ||
| US4409369A (en) | 1980-03-03 | 1983-10-11 | The Dow Chemical Company | Transparent impact resin and process for the preparation thereof |
| US4572819A (en) | 1983-08-24 | 1986-02-25 | The Dow Chemical Company | Apparatus for anionic polymerization wherein the molecular weight of the polymer is closely controlled |
| US4585825A (en) | 1983-09-30 | 1986-04-29 | The Dow Chemical Company | Monovinylidene aromatic polymer resins having added amounts of high molecular weight polymer |
| US4666987A (en) | 1985-02-22 | 1987-05-19 | The Dow Chemical Company | In-mold polymerization of vinyl aromatic compound |
| US5272236A (en) | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
| JPH04130106A (en) * | 1990-09-21 | 1992-05-01 | Japan Synthetic Rubber Co Ltd | Thermoplastic elastomer composition |
| US5278272A (en) | 1991-10-15 | 1994-01-11 | The Dow Chemical Company | Elastic substantialy linear olefin polymers |
| JP3318983B2 (en) * | 1992-09-18 | 2002-08-26 | ジェイエスアール株式会社 | Ethylene-propylene copolymer rubber composition |
| US5608023A (en) * | 1995-03-30 | 1997-03-04 | Xerox Corporation | Rate enhanced polymerization processes |
| DE59710063D1 (en) * | 1996-02-01 | 2003-06-18 | Borealis Gmbh Schwechat Mannsw | Structural Isomeric Poly (alkylethylene) |
| US6031012A (en) * | 1996-05-15 | 2000-02-29 | Kaneka Corporation | Curable composition, foam produced therefrom, and process for producing the foam |
| EP0909280B1 (en) * | 1996-06-26 | 2000-08-23 | Ciba SC Holding AG | Decomposing polymers using nor-hals compounds |
| FR2754535A1 (en) * | 1996-10-16 | 1998-04-17 | Atochem Elf Sa | GRAFTED POLYMERS WITH CONTROLLED VISCOSITY |
| JP3389093B2 (en) * | 1997-04-11 | 2003-03-24 | 株式会社日本触媒 | Thermoreversible crosslinked polymer and its use |
| FR2768739B1 (en) * | 1997-09-19 | 2004-08-06 | Atochem Elf Sa | SHOCK VINYLAROMATIC POLYMER OBTAINED FROM A RUBBER CARRIER OF A GROUP GENERATING A STABLE FREE RADICAL |
| FR2779437B1 (en) * | 1998-06-03 | 2004-10-15 | Atochem Elf Sa | VINYLAROMATIC POLYMER SHOCK BY POLYMERIZATION OF A VINYLAROMATIC MONOMER IN THE PRESENCE OF A STABLE FREE RADICAL AND A POLYMERIZATION PRIMER |
| JP2000143732A (en) * | 1998-08-31 | 2000-05-26 | Yokohama Rubber Co Ltd:The | Free radical-containing isobutylene polymer and rubber composition containing the same |
| CN1272380C (en) * | 1998-10-08 | 2006-08-30 | 钟渊化学工业株式会社 | Curable compositions |
| FR2792321B1 (en) * | 1999-04-19 | 2003-12-12 | Atochem Elf Sa | PROCESS FOR PRODUCING POLYPROPYLENE RESIN WITH CONTROLLED RHEOLOGY |
| JP4608725B2 (en) * | 2000-04-10 | 2011-01-12 | 横浜ゴム株式会社 | Thermoplastic elastomer and composition thereof |
| JP2001279108A (en) * | 2000-01-28 | 2001-10-10 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
| EP1264857B1 (en) * | 2000-01-28 | 2008-01-09 | Kaneka Corporation | Curable composition |
| FR2805268B1 (en) * | 2000-02-23 | 2005-03-25 | Atofina | THERMOREVERSIBLE POLYMERS WITH MITROXIDE FUNCTIONS |
| JP3565773B2 (en) * | 2000-09-06 | 2004-09-15 | 日本ユニカー株式会社 | Electric insulating resin composition and electric wire / cable coated therewith |
| JP4001497B2 (en) * | 2001-02-26 | 2007-10-31 | 横浜ゴム株式会社 | Radical modified polymer and polymer composition containing the same |
| DE60219948T2 (en) | 2001-11-06 | 2007-09-06 | Dow Global Technologies, Inc., Midland | FIBERS OF ISOTAKTIC PROPYLENE COPOLYMERISATE, THEIR PREPARATION AND USE |
| JP4197261B2 (en) * | 2002-02-28 | 2008-12-17 | 株式会社ジェイエスピー | POLYPROPYLENE RESIN FOAM PARTICLE, POLYPROPYLENE RESIN FOAM PARTICLE MOLDED BODY, AND METHOD FOR PRODUCING POLYPROPYLENE RESIN FOAM PARTICLE |
-
2004
- 2004-12-24 EP EP09000423A patent/EP2050793A3/en not_active Withdrawn
- 2004-12-24 CN CN2004800388878A patent/CN1898337B/en active Active
- 2004-12-24 WO PCT/US2004/043342 patent/WO2005063895A2/en not_active Application Discontinuation
- 2004-12-24 WO PCT/US2004/043354 patent/WO2005066281A2/en not_active Application Discontinuation
- 2004-12-24 CA CA002550953A patent/CA2550953A1/en not_active Abandoned
- 2004-12-24 EP EP04815432A patent/EP1699882B1/en not_active Not-in-force
- 2004-12-24 CN CNA2004800388863A patent/CN1898336A/en active Pending
- 2004-12-24 JP JP2006547380A patent/JP2007517120A/en active Pending
- 2004-12-24 CA CA002551013A patent/CA2551013A1/en not_active Abandoned
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- 2004-12-24 CN CN2011101150074A patent/CN102268154A/en active Pending
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- 2004-12-24 AT AT04815420T patent/ATE409729T1/en not_active IP Right Cessation
- 2004-12-24 EP EP04815420A patent/EP1699879B1/en not_active Not-in-force
- 2004-12-24 CN CNA2004800419698A patent/CN1918236A/en active Pending
- 2004-12-24 US US11/021,955 patent/US20050197457A1/en not_active Abandoned
- 2004-12-24 JP JP2006547377A patent/JP2007517118A/en active Pending
- 2004-12-24 JP JP2006547381A patent/JP2007517121A/en active Pending
- 2004-12-24 JP JP2006547375A patent/JP2007517117A/en active Pending
- 2004-12-24 EP EP04815433A patent/EP1699883A2/en not_active Withdrawn
- 2004-12-24 BR BRPI0417753-3A patent/BRPI0417753A/en not_active IP Right Cessation
- 2004-12-24 US US10/583,299 patent/US20070173613A1/en not_active Abandoned
- 2004-12-24 CN CNA2004800389870A patent/CN1898339A/en active Pending
- 2004-12-24 WO PCT/US2004/043355 patent/WO2005066282A2/en not_active Application Discontinuation
- 2004-12-24 AT AT04815432T patent/ATE442420T1/en not_active IP Right Cessation
- 2004-12-24 EP EP04815424A patent/EP1699880A2/en not_active Withdrawn
- 2004-12-24 DE DE602004016886T patent/DE602004016886D1/en active Active
- 2004-12-24 CA CA002550763A patent/CA2550763A1/en not_active Abandoned
- 2004-12-24 KR KR1020067012665A patent/KR20060135679A/en active IP Right Grant
- 2004-12-24 CN CNA2004800385901A patent/CN1898335A/en active Pending
- 2004-12-24 WO PCT/US2004/043346 patent/WO2005063896A2/en not_active Application Discontinuation
- 2004-12-24 TW TW093140668A patent/TW200602413A/en unknown
- 2004-12-24 TW TW093140663A patent/TW200535181A/en unknown
- 2004-12-24 CA CA002551015A patent/CA2551015A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040059060A1 (en) * | 1999-09-16 | 2004-03-25 | Keisuke Chino | Thermo-reversible, crosslinkable elastomer and composition thereof |
| CN1527815A (en) * | 2001-05-17 | 2004-09-08 | ���з��ɹ�˾ | Organic peroxide heat stabliser |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059250A (en) * | 2013-01-08 | 2013-04-24 | 南开大学 | Novel reversible covalent cross-linked thermoplastic polyurethane |
| CN103059250B (en) * | 2013-01-08 | 2014-11-05 | 南开大学 | Novel reversible covalent cross-linked thermoplastic polyurethane |
| CN104884508A (en) * | 2013-03-06 | 2015-09-02 | 积水化学工业株式会社 | Resin-composite-material production method, and resin composite material |
| CN108017728A (en) * | 2016-11-01 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of rubber composition, the modified rubber with self-healing function and its preparation method and application |
| CN108017728B (en) * | 2016-11-01 | 2021-04-13 | 中国石油化工股份有限公司 | Rubber composition, modified rubber with self-healing function and preparation method and application thereof |
| CN111148628A (en) * | 2017-09-30 | 2020-05-12 | 陶氏环球技术有限责任公司 | Air-curable ethylene/α -olefin/diene interpolymer compositions |
| CN111148628B (en) * | 2017-09-30 | 2023-03-31 | 陶氏环球技术有限责任公司 | Air-curable ethylene/alpha-olefin/diene interpolymer compositions |
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